JP5106786B2 - Detergent composition for dishwasher - Google Patents

Description

  The present invention relates to a detergent composition for use in a dishwasher. In particular, the present invention relates to a detergent composition for use in a commercial dishwasher.

  A dishwasher is a facility for washing dishes such as dirty dishes, glasses and cooking utensils, and is used in kitchens such as homes, restaurants and coffee shops. In general, dishwashing is performed in the order of washing process-rinsing process. In the washing process, a non-foaming or low-foaming dishwasher cleaner different from a dishwashing detergent for hand washing is used. In addition, a rinsing agent is used in the rinsing process for commercial dishwashers used in kitchens such as restaurants and coffee shops.

  Rinse agents are used to speed up the drying of dishes and reduce the appearance of white spots called water spots for a beautiful finish. The water spot is dried before water droplets adhering to the tableware surface flow down, and hardness components such as calcium, magnesium, and silica are deposited on the tableware surface.

  Generally, nonionic surfactants such as glycerin fatty acid esters and sorbitan fatty acid esters are blended in the rinsing agent, and the rinse water is emulsified to lower the surface tension with the tableware and make it easy for water droplets to flow down. As a result, the drying of the tableware is accelerated, and the water spot can be reduced. Therefore, rinsing agents are used in restaurants and coffee shops where tableware is frequently used.

  However, although the rinse agent has an effect of reducing the water spot, it is never satisfactory. In particular, since the plastic tableware surface is hydrophobic, it is difficult to reduce the surface tension with the tableware with the current rinse agents, and many of them are inferior in the effect of reducing water spots. Further, since the rinse agent is used in the rinsing process, a supply device different from the cleaning agent used in the cleaning process is required. Furthermore, it is necessary to purchase rinsing agents and inventory management costs, which is a big burden at restaurants and coffee shops.

Patent Document 1 contains a positively charged polymer, a water-soluble polymer that suppresses phosphate scale formation, and exhibits excellent cleaning effect and glass appearance even in the absence of sodium chloride or a rinse aid composition. A composition is disclosed. Patent Documents 2 and 3 disclose that a cationic or amphoteric polymer is used as a detergent for a dishwasher. Patent Documents 4 and 5 disclose the use of amphoteric polymers as cleaning agents for dishwashers.
JP-T-2004-508456 WO99 / 58633 pamphlet European Patent Application No. 0835925 Special table 2003-505535 gazette JP 2005-527686 Gazette

  The object of the present invention is to clean a dishwasher that is excellent in cleaning performance and can speed up drying of tableware and reduce water spots without using a rinse agent in the cleaning of tableware such as ceramics, glass, and plastic. It is to provide an agent composition. In particular, an object of the present invention is to provide a cleaning composition for a dishwasher that accelerates drying of plastic tableware and enables reduction of water spots.

  The present invention relates to (A) a structural unit (a1) represented by the following general formula (1), a structural unit (a2) represented by the following general formula (2), and the following general formula (3). A water-soluble polymer compound (hereinafter referred to as component (A)), (B) a surfactant (hereinafter referred to as component (B)), and (C) a builder [containing a structural unit (a3) represented by Hereinafter, it is referred to as a component (C)].

[Wherein, R is an alkyl group having 1 to 3 carbon atoms, and X is a structural unit derived from an unsaturated compound having a cationic group in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester. ]

  According to the present invention, when used for washing tableware such as ceramics, glass, plastic, etc., it is excellent in cleaning properties, and it is possible to speed up drying of tableware and reduce water spots without using a rinse agent in rinsing water etc. A dishwasher cleaning composition is provided. In particular, there is provided a detergent composition for a dishwasher that accelerates drying of plastic tableware and enables reduction of water spots.

<(A) component>
The water-soluble polymer compound (A) having the structural unit (a1), the structural unit (a2), and the structural unit (a3) is composed of the monomer compound and the structural unit (a3) from which the structural unit (a2) is derived. ) Is obtained by copolymerization with a saponification partly. For example, as a polymer compound in which R in the general formula (2) is a methyl group, a copolymer of a polymerizable cationic monomer (a compound from which the structural unit (a3) is derived) and vinyl acetate is partially saponified. The cationized polyvinyl alcohol obtained by this can be used.

  The molar ratio of the structural unit (a1) and the structural unit (a2) is such that (a1) / (a2) is 1,000 to 1, more preferably 500 to 1, more preferably 300 to 1, from the viewpoint of solubility and finish. In particular, 200-1 and most preferably 100-2 are preferred.

  Here, the monomer compound from which the structural unit (a3) is derived has one or more cationic groups in the molecule, and is a vinyl alcohol lower (carbon number 1 to 3) fatty acid ester (structural unit (a1)). , A monomer compound derived from (a2)), a compound copolymerizable with the compound represented by the following general formula (3-1) and the compound represented by the following general formula (3-2) Examples include selected compounds.

[Wherein, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X, Y each independently, an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

  Specific monomer compounds derived from the structural unit (a3) include diallyldialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salt, N- (meth) acryloylaminoalkyl (carbon of the alkyl group) The number is 1-5) -N, N-dialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salt, N- (meth) acryloylaminoalkyl (the alkyl group has 1 to 5 carbon atoms) -N, N, N-trialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salt, N- (meth) acryloyloxyalkyl (the alkyl group has 1 to 5 carbon atoms) -N, N, N-trialkyl (The alkyl group has 1 to 3 carbon atoms) ammonium salt and N- (ω-alkenyl (the alkenyl group has 2 to 10 carbon atoms))-N, N-dialkyl (the alkyl group has 1 to 3 carbon atoms) 3) Choose from ammonium salts That compound, and the like.

  Among the structural units of the component (A), the total of the structural unit (a1), the structural unit (a2) and the structural unit (a3) is 50 to 100 mol%, more preferably 60 to 100 mol%, particularly from the viewpoint of finish. 80-100 mol% is preferable.

  Among the structural units of the component (A), the structural unit (a3) containing a cationic group is 0.001 to 10 mol%, more preferably 0.005 to 5 mol%, particularly 0.01 to 3 mol from the viewpoint of finish. % Is preferred.

  The component (A) can also contain a structural unit derived from a nonionic monomer (hereinafter referred to as “structural unit (a4)”). Examples of the structural unit (a4) include monomers selected from the following (i) to (iii).

  (I) Acrylic (or methacrylic) amide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic) Acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound

  (Ii) Acrylic acid (or methacrylic acid) alkyl (carbon number 1 to 5), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (carbon number 1) -5), an ester group-containing compound selected from dialkyl maleates (having 1 to 5 carbon atoms)

  (Iii) ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl Olefin compounds selected from -1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene

  The weight average molecular weight of the component (A) is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 200,000. The weight average molecular weight here can be determined by gel permeation chromatography using polyethylene glycol as a standard.

<(B) component>
As the component (B), one or more selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, alkyl sulfate ester, polyoxyethylene (average number of added moles 1 to 10) alkyl ether sulfate, polyoxy Examples include ethylene (average number of added moles of 1 to 10) alkyl ether acetate, fatty acid salt and the like. The salt is preferably an ammonium salt, sodium salt or potassium salt.

  Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylammonium salt, benzalkonium salt, benzethonium salt, imidazolium salt, pyridinium salt and the like. The salt is preferably a halogen.

  Examples of the amphoteric surfactant include alkyldimethylamine oxide, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, alkylamidopropylbetaine, alkylcarboxymethylhydroxyethylimidazolium betaine and the like.

  Nonionic surfactants include glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkylpolyglucoside, polyoxyethylene Examples include alkyl ether, polyoxyethylene dialkyl ether, polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxypropylene polyoxyethylene polyoxypropylene glycol and the like.

As the component (B), a nonionic surfactant represented by the following formula (4) [hereinafter referred to as the component (B1)] is preferable from the viewpoint of low foaming properties and detergency.
_{^{R 14 - (AO) n -R}} 15 (4)
[Wherein, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms. n is an average addition mole number, and is a number of 1-500. A is the same or different and is an ethylene group, a propylene group, or a butylene group. ]

In the component (B1), R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom or a linear or branched alkyl group having 6 to 18 carbon atoms, more preferably a hydrogen atom, or a linear or branched chain. These are alkyl groups having 8 to 14 carbon atoms. n is an average addition mole number, Preferably it is 1-400, More preferably, it is 1-350, More preferably, it is 1-200, Most preferably, it is a number of 1-100. A is the same or different and is preferably an ethylene group or a propylene group. Component (B1) is available from BASF under the trade name “Plurafac”.

Furthermore, from the viewpoint of detergency, non-foaming property and low-foaming property, as the component (B), a nonionic surfactant represented by the following formula (5) and a nonionic surfactant represented by the formula (6) One or more nonionic surfactants selected from the group consisting of agents (hereinafter referred to as component (B2)) are preferred.
HO (CH ₂ CH ₂ O) _a (CH (CH ₃ ) CH ₂ O) _b (CH ₂ CH ₂ O) _c H (5)
HO (CH (CH ₃ ) CH ₂ O) _d (CH ₂ CH ₂ O) _e (CH (CH ₃ ) CH ₂ O) _f H (6)
[Wherein, a, b, c, d, e and f are the average number of moles added, each independently a number of 1 to 350. ]

  In the general formulas (5) and (6), a, b, c, d, e and f are the average added moles of ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO). Yes, each independently a number from 1 to 350.

  The component (B2) preferably contains 10 mol% or more of EO in the total of EO and PO, and a, b, c, d, e and f are preferably selected so as to satisfy this.

  Moreover, 1,000-15,000 are preferable and, as for the weight average molecular weight of (B2) component, More preferably, it is 1,500-6,000. The component (B2) is available from BASF under the trade names “Pluronic” and “Pluronic R”. As the component (B2), a nonionic surfactant represented by the formula (5) is preferable from the viewpoint of low foamability.

<(C) component>
As the action of the component (C), a metal chelate action, an alkali buffer action and a solid particle dispersing action are important.

  Examples of the inorganic component (C) include carbonates, phosphates, silicates, sulfates, and the like. Specific examples include sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium orthophosphate, sodium hexametaphosphate, sodium sulfate, sodium silicate, potassium silicate, and sodium metasilicate.

  As the organic component (C), (i) ethane-1,1-diphosphonic acid, ethane-1,2-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy- Salts of phosphonic acids such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, (b) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid, (ha) salts of amino acids such as aspartic acid and glutamic acid, (d) nitrilotriacetate, Aminopolyacetates such as ethylenediaminetetraacetate, (e) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane , 2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, oxalic acid, sulfosuccinic acid Examples thereof include salts of organic acids such as acids, malic acid, and gluconic acid, (f) polyacrylic acid salts, acrylic acid-maleic acid copolymers, and salts thereof.

  As the component (C), from the viewpoints of detergency, sequestering ability, and anti-recontamination property, sodium carbonate, potassium carbonate, sodium tripolyphosphate, sodium sulfate, sodium silicate, sodium metasilicate, ethane-1-hydroxy- Sodium 1,1-diphosphonate, sodium ethylenediaminetetraacetate, sodium citrate, and polyacrylic acid / sodium polymaleate copolymer are preferred.

  The detergent composition for a dishwasher of the present invention preferably contains an enzyme [hereinafter referred to as component (D)] from the viewpoint of detergency.

<(D) component>
Specific examples of the component (D) include cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase. Protease and amylase are particularly preferable from the viewpoint of detergency.

  Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, everase, cannase, esperase (manufactured by Novo Nordisk Bioindustry), ovozyme, plate, propellase, and plate OX (manufactured by Genencor International).

  Examples of commercially available enzymes that can be used as amylase include Lapidase (manufactured by Gist-Brokers), Termamyl, Duramil, Steinzyme (manufactured by Novo Nordisk Bioindustry), Plaster ST, and Plaster OxAm.

  In the detergent composition for a dishwasher of the present invention, protease and amylase can be used in combination. The weight ratio of amylase / protease as the amount of enzyme protein is preferably 1/99 to 94/6, more preferably 2/98 to 90/10, still more preferably 20/80 to 80/20 from the viewpoint of detergency. is there.

<Cleaning composition for dishwasher>
In the detergent composition for a dishwasher of the present invention, the component (A) is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, from the viewpoint of finish. More preferably 0.1 to 3% by weight. Particularly preferably, the content is 0.5 to 2% by weight.

  In the detergent composition for a dishwasher of the present invention, the component (B) is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight, and still more preferably 0, from the viewpoint of detergency. 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight.

  The dishwasher cleaning composition of the present invention is preferably used as a cleaning liquid diluted to an appropriate concentration with water or the like in use, and the concentration of the component (A) in the cleaning liquid From the viewpoint, it is preferably 0.1 to 1,000 ppm (weight ratio), more preferably 0.5 to 500 ppm, still more preferably 1 to 300 ppm, and particularly preferably 3 to 100 ppm. The concentration of the component (B) in the cleaning liquid is preferably 0.1 to 1,000 ppm, more preferably 0.5 to 500 ppm, still more preferably 1 to 100 ppm, and particularly preferably 5 from the viewpoint of cleaning power. -50 ppm.

  In the detergent composition for a dishwasher of the present invention, the component (C) is preferably 16 to 95% by weight, more preferably 20 to 95, from the viewpoints of detergency, sequestering ability, and recontamination prevention. It is contained by weight% or more, particularly preferably 40 to 95% by weight, most preferably 60 to 95% by weight.

  Further, the concentration of the component (C) in the cleaning liquid is 50 ppm or more (weight ratio) from the viewpoint of sequestering properties, preferably 80 ppm or more, more preferably 100 ppm or more, still more preferably 150 ppm or more, particularly preferably. 200 ppm or more, most preferably 250 ppm or more.

  In the detergent composition for a dishwasher of the present invention, the component (D) is preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight, and still more preferably 0, from the viewpoint of detergency. .Contains 2 to 5% by weight. Further, the concentration of the component (D) in the cleaning liquid during use is preferably 0.1 to 500 ppm (weight ratio), more preferably 0.5 to 200 ppm, still more preferably 1 to 100 ppm, from the viewpoint of cleaning properties. Most preferably, it is 5-80 ppm.

  It is preferable that the cleaning composition for dishwashers of this invention contains (D) component as the granulated particle. The amount of enzyme protein in the particles is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, from the viewpoint of storage stability. The average particle diameter of the particles is preferably 50 to 1,000 μm, more preferably 150 to 800 μm.

  In the detergent composition for a dishwasher of the present invention, the weight ratio of the component (A) to the component (B) is preferably 20/1 to 1/20, more preferably 10 / 1 to 1/10, 5/1 to 1/10, most preferably 3/1 to 1/10 are preferable.

  It is preferable that the pH of the 0.2 weight% aqueous solution in 20 degreeC of the cleaning composition for dishwashers of this invention is 5-14. From the viewpoint of work safety, 5.5 to 12 is preferable, and 6.5 to 11 is more preferable. In addition, if pH becomes in the range of 5-14, you may mix | blend pH adjusters, such as sodium hydroxide and potassium hydroxide sulfuric acid.

  The cleaning composition for a dishwasher of the present invention can contain an organic polymer compound. Specifically, dextrin derived from natural products, carrageenan, xanthan gum, guar gum, pectin, locust bin gum, or derivatives thereof, modified starch, methylcellulose, carboxymethylcellulose and other polysaccharides, cationized guar gum, cationized gum arabic, cationized Examples include cationic polysaccharides such as starch, cationized chitosan, and cationized cellulose. In addition, synthetic polymer compounds such as polyvinyl alcohol, polyacrylamide, and polyethylene oxide can be used. From the viewpoint of storage stability, these are preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and still more preferably 1 to the detergent composition for dishwashers of the present invention. -10% by weight.

  The cleaning composition for a dishwasher of the present invention can contain a water-insoluble inorganic powder as a surface modifier. The primary particle size of the water-insoluble inorganic powder is preferably 5 nm to 200 μm, more preferably 20 nm to 100 μm, and still more preferably 20 nm to 50 μm, from the viewpoint of storage stability. Specifically, crystalline silicate, aluminosilicate, silica, and alumina are preferable. The content of the water-insoluble inorganic powder in the dishwasher detergent composition is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, from the viewpoint of storage stability. More preferably, it is 0.1-6 weight%, Most preferably, it is 0.5-5 weight%.

  When silica is used as the water-insoluble inorganic powder, Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Toxeal, Fine Seal, Leorosil (manufactured by Tokuyama Co., Ltd.), Silo Pure (manufactured by Fuji Silysia Chemical Co., Ltd.), etc. It is preferable to use it.

  In addition, bleaching agents, antifoaming agents, rust preventives, preservatives, hydrotropes, fragrances, water, and the like can be contained.

  As the above components, those described in International Publication No. 99/58633 pamphlet can be referred to.

  In the case of washing with a commercial dishwasher using the detergent composition for a dishwasher of the present invention, the composition is arbitrarily transferred into a commercial dishwasher by a supply device, and the proper composition is transferred. The concentration of the cleaning solution is maintained. A dishwasher cleaning composition that is set in a predetermined direction for each container of plastic or the like filled with a detergent composition for dishwashers in a dedicated hopper for commercial dishwashers or filled in a pouch container or the like Is transferred to a dedicated dishwasher hopper, sprayed with water or hot water onto the dishwasher cleaning composition by spraying or showering, etc., and the dissolved cleaning solution is supplied into the commercial dishwasher.

  The cleaning composition for a dishwasher of the present invention is used at a concentration of 0.01 to 0.5% by weight in the cleaning liquid, but from the viewpoint of economy and cleaning properties, 0.01 to 0.3% by weight. % Is preferable, and 0.03 to 0.25% by weight is more preferable. The washing time for tableware is preferably 10 seconds to 3 minutes, more preferably 20 seconds to 2 minutes, from the viewpoint of detergency. The cleaning temperature of the cleaning liquid is very important for improving the cleaning performance in a short time, and is preferably 40 ° C. or more, and particularly preferably 40 to 70 ° C. After the dishes are washed, they are usually rinsed quickly with water, warm water or hot water at 70-90 ° C. in the same commercial dishwasher. Since the cleaning composition for a dishwasher of the present invention can accelerate the drying of dishes and reduce water spots without using a rinse agent, rinsing is performed with water, hot water, or 70-90. It can be performed only with hot water at ℃.

  In the case of continuously washing dishes with a commercial dishwasher, the concentration of the washing liquid decreases with the number of washings due to carry-out of the washing liquid by tableware or carry-over of rinsing water to the washing tank. In order to maintain an appropriate concentration of the cleaning liquid, the dishwasher cleaning composition is supplied to an appropriate concentration by an automatic supply device.

  The automatic supply device for the detergent composition for a dishwasher is not particularly limited, but it senses the concentration of the cleaning solution, receives a signal, and sprays water or hot water in the form of a spray or shower. Spray the cleaning composition to supply the required amount of the cleaning composition for a dishwasher.

  This automatic supply device is preferably used for business use with a very large number of cleanings per day, and has the advantage that it saves a lot of time compared to manual feeding for each cleaning frequency. It becomes easy to maintain a proper concentration in the middle (during washing).

  According to the present invention, there is provided a tableware cleaning method in which tableware is washed by a dishwasher using the detergent composition for a dishwasher of the present invention and then rinsed with rinsing water containing no rinse agent. Provided.

  A detergent composition for a dishwasher having the composition shown in Table 1 was prepared, and the washability and finishability (drying speed and water spot) were evaluated by the following methods. The results are shown in Table 1.

[1] Preparation of model dirt ・ Production of model dirt for plastic tableware On the center of a new 20 cm diameter melamine resin dish, 4 g of egg yolk is uniformly applied in a circular shape with a brush of about 16 cm in diameter and set to 80 ° C. Put in an electric dryer. After 30 minutes, the melamine resin dish coated with egg yolk was taken out, and the naturally cooled one was used as a model soil for evaluation of detergency and finish.

-Preparation of glass model stains After applying 2g of milk to a new 10 ounce glass, the ones dried at 60 ° C for 2 hours were used as model stains to evaluate the finished quality.

[2] Detergency Evaluation / Evaluation Method 19 g of the detergent composition for dishwasher was put into a washing tank (38L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] Dissolved. Four melamine resin dishes coated with model dirt on a dedicated rack were set, washed with a cleaning solution at 50 ° C. for 50 seconds, and then rinsed with rinsing water at 90 ° C. for 10 seconds without using a rinse agent. . The melamine resin dish was taken out from the dedicated rack, colored with a 1% by weight aqueous solution of erythrosine dye, and the detergency was evaluated according to the following criteria.

* Judgment criteria for cleanability ◎: No coloring marks are observed, dirt is completely removed ○: Slight coloring marks are observed, but most dirt is removed Δ; Residual x: Mostly colored marks are observed and a lot of dirt remains.

  The results are shown in Table 1. It was revealed that the detergent composition for a dishwasher of the present invention is excellent in detergency.

[3] Finishing property evaluation / evaluation method 1
19 g of the detergent composition for a dishwasher was put into a washing tank (38 L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] and dissolved in hot water at 50 ° C. Four melamine resin dishes coated with model dirt on a dedicated rack were set, washed with a cleaning solution at 50 ° C. for 50 seconds, and then rinsed with rinsing water at 90 ° C. for 10 seconds without using a rinse agent. . The melamine resin dish was taken out from the dedicated rack and dried at 25 ° C. The finishing criteria related to the drying speed and water spot were evaluated according to the following criteria.

* Criteria for drying speed (1)
◎; Average per dish dried in less than 1 hour ○; Average per dish over 1 hour and less than 1 hour 30 minutes Δ; Average per dish 1 hour 30 minutes Above, drying in less than 2 hours ×; drying on average over 2 hours per dish

* Water spot judgment criteria (1)
◎: The average number of water spots is less than 10 per dish. ○: The average number of water spots is 10 or more and less than 20 per dish. △; The number of water spots is the average per dish. 20 or more and less than 40 ×: The number of water spots is an average of 40 or more per dish

・ Evaluation method 2
19 g of the detergent composition for a dishwasher was put into a washing tank (38 L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] and dissolved in hot water at 50 ° C. Four 10-ounce glasses coated with model dirt were set on a dedicated rack, washed with a cleaning solution at 50 ° C. for 50 seconds, and then rinsed with rinsing water at 90 ° C. for 10 seconds without using a rinse agent. An 8 ounce glass was taken out from the dedicated rack and dried at 25 ° C. The finishing criteria related to the drying speed and water spot were evaluated according to the following criteria.

* Criteria for drying speed (2)
◎: Average drying per glass for less than 1 hour ○; Average drying per glass for 1 hour or more, less than 1 hour 30 minutes Δ; Average per glass 1 hour 30 minutes Above, dry in less than 2 hours ×; dry on average over 2 hours per glass

* Water spot judgment criteria (2)
◎: The number of water spots is less than 10 on average per glass ○: The number of water spots is on average 10 or more per glass △: The average number of water spots is per glass 20 or more and less than 40 ×; the number of water spots is 40 or more on average per glass

  The results are shown in Table 1. It became clear that the cleaning composition for dishwashers of the present invention accelerates drying and reduces water spots without using a rinse agent in the rinsing water.

(Note) The components in the table are as follows.
Water-soluble polymer compound (1): (a1) vinyl alcohol: 86.8 mol%, (a2) vinyl acetate: 12.3 mol%, (a3) diallyldimethylammonium chloride: 0.9 mol%, (a1 ) / (A2) = 7.1, (a1) + (a2) + (a3) = 100 mol%
Water-soluble polymer compound (2): (a1) vinyl alcohol: 99 mol%, (a2) vinyl acetate: 0.7 mol%, (a3) methacrylamidopropyltrimethylammonium chloride: 0.3 mol%, (a1 ) / (A2) = 141.4, (a1) + (a2) + (a3) = 100 mol%
Water-soluble polymer compound (3): (a1) vinyl alcohol: 88.5 mol%, (a2) vinyl acetate: 9.8 mol%, (a3) methacrylamidopropyltrimethylammonium chloride: 1.7 mol%, (A1) / (a2) = 9.0, (a1) + (a2) + (a3) = 100 mol%
Water-soluble polymer compound (4): (a1) vinyl alcohol: 77 mol%, (a2) vinyl acetate: 22.95 mol%, (a3) methacrylamidopropyltrimethylammonium chloride: 0.05 mol%, (a1 ) / (A2) = 3.4, (a1) + (a2) + (a3) = 100 mol%
・ Nonionic surfactant (1): PO / EO / PO block polymer, Pluronic RPE2520 (BASF)
Nonionic surfactant (2): aliphatic alcohol alkoxylate, Plurafac LF403 (manufactured by BASF)
Nonionic surfactant (3): branched chain aliphatic alcohol alkoxylate, Softanol 70H (manufactured by Nippon Shokubai Co., Ltd.)
・ Acrylic acid / maleic acid copolymer, sodium salt (1): Sokalan CP5 Granules (BASF)
Enzyme (1): Amylase (Termamyl 60T, manufactured by Novo Nordisk Bioindustry)

Claims (7)

(A) The structural unit (a1) represented by the following general formula (1), the structural unit (a2) represented by the following general formula (2), and the structural unit (a3 represented by the following general formula (3) ) Containing a water-soluble polymer compound, (B) a surfactant, and (C) a builder ,
In the structural unit (A), the total of the structural unit (a1), the structural unit (a2), and the structural unit (a3) is 80 to 100 mol%.
The molar ratio (a1) / (a2) of the structural unit (a1) and the structural unit (a2) of (A) is 200 to 1,
In the structural unit (A), the structural unit (a3) is 0.001 to 10 mol%.
A detergent composition for dishwashers.

[Wherein, R is an alkyl group having 1 to 3 carbon atoms, and X is a structural unit derived from an unsaturated compound having a cationic group in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester. ] In the structural unit (A), the structural unit (a3) is derived from a compound selected from a compound represented by the following general formula (3-1) and a compound represented by the following general formula (3-2) The cleaning composition for a dishwasher according to claim 1 .

[Wherein, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X, Y each independently, an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ] The (A) water-soluble polymer compound is contained in an amount of 0.01 to 10% by weight, the surfactant (B) in an amount of 0.01 to 50% by weight, and the builder (C) in an amount of 16 to 95% by weight. Or the detergent composition for dishwashers of 2 . Furthermore, (D) The cleaning composition for dishwashers in any one of Claims 1-3 containing an enzyme . (D) The detergent composition for dishwashers according to claim 4, wherein the enzyme is an enzyme selected from protease and amylase. The weight ratio of said (A) water-soluble polymer compound and said (B) surfactant is 20/1-1/20 in (A) / (B), The any one of Claims 1-5. Detergent composition for dishwashers. Tableware washing | cleaning which wash | cleans tableware with a dishwasher using the cleaning composition for dishwashers of any one of Claims 1-6 , and performs a rinsing process with the rinse water which does not contain a rinse agent after that. Method.